Messi's dazzling display
Villarreal took the lead in La Liga after they won 2-0 at Racing Santander on Wednesday.
First half goals from Turkish international Nihat Kahveci and their American-born Italian striker Guiseppe Rossi secured pole position on goal difference from local rivals Valencia, who laboured to a 2-1 win over Getafe.
The two teams both have 12 points from their five games, with unbeaten Barcelona one point further back after inflicting a 4-1 thrashing on Real Zaragoza.
However, Villarreal's lead may only last a little over 24 hours as Real Madrid, who started the week on top, have a game in hand and play host to struggling Real Betis on Thursday.
The unbeaten reigning Spanish champions need only to draw with Betis, who have yet to win this season, to leapfrog over the three teams who are ahead of them.
After Racing had several good early chances, Kahveci broke the deadlock six minutes before half time after a superb pass from the right flank by Chilean winger Matias Fernandez.
Racing were reduced to 10 men on 62 minutes after defender Aldo Duscher was dismissed for a wild tackle on Cani Garcia.
Guiseppe Rossi then secured three points for the visitors when he scored, his fourth goal of the season, from a Robert Pires pass after 76 minutes.
"Duscher's sending off wasn't decisive. Our effectiveness was," reflected Villarreal coach Manuel Pellegrini.
"This was a very good victory against a team that was waiting for us, a team that had only lost once and that against a very good team before we met them," added the Chilean coach.
Valencia were made to work hard for their fourth successive win but eventually triumphed after first half goals from Spanish internationals David Silva and David Villa.
Silva opened the scoring after 15 minutes, jumping on the ball after Getafe goalkeeper Oscar Ustari failed to properly clear a Fernando Morientes shot.
Villa, last season's top domestic scorer with 16 goals, then got his first of this season on the half hour when he hammered home a pass from Valencia captain David Albelda.
Getafe midfielder Braulio Nobrega got one back but, despite some late pressure, the visitors from Madrid could not quite salvage a draw.
"We gave away the two goals and that makes life difficult however well you play after that," said Getafe's under-fire coach Michael Laudrup.
The result means that Getafe are still without a win this season and are just one place off the bottom of the Spanish first division.
Barcelona produced their best performance of the season to unravel Real Zaragoza with four first half goals.
Argentine winger Lionel Messi found the net after just five minutes but Zaragoza's Alberto Zapater equalised four minutes later.
However, the 2006 European champions quickly got back into their stride and Messi took barely a minute before he sent a cross from Deco into the back of the net to give Barca the lead again.
Andres Iniesta and Rafa Marquez added more goals before the break before the Catalan club stepped off the gas in the second half.
Thierry Henry once again disappointed and - with the crowd chanting 'Ronaldinho, Ronaldinho' and clamouring for the return of the Brazilian - squandered several chances late in the game despite the best efforts of his team mates to set him up with a gilt-edged goal scoring chance.
Osasuna got their first win of the season with an emphatic 4-1 defeat of bottom club Levante.
Uruguayan striker Walter Pandiani put the hosts ahead with a header after 31 minutes, connecting with a Jose Izquierdo cross from the right wing, but Levante equalised through Felix Ettien just three minutes later.
Pandiani then put Osasuna back in front six minutes after the break and Juanfran Torres added the Pamplona-based side's third from the edge of the area just before the hour.
Javi Garcia finished off the thrashing 14 minutes from time to leave Levante continuing to prop up the Spanish first division with just a solitary point to their name.
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